US20190177605A1 - Multifunctional single component systems and methods for sandstone acidizing - Google Patents

Multifunctional single component systems and methods for sandstone acidizing Download PDF

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US20190177605A1
US20190177605A1 US16/324,036 US201616324036A US2019177605A1 US 20190177605 A1 US20190177605 A1 US 20190177605A1 US 201616324036 A US201616324036 A US 201616324036A US 2019177605 A1 US2019177605 A1 US 2019177605A1
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treatment fluid
acid
fluid
formation
sandstone formation
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Sairam ELURU
Vijaya Kumar Patnana
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Halliburton Energy Services Inc
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/72—Eroding chemicals, e.g. acids
    • C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C09K8/528—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning inorganic depositions, e.g. sulfates or carbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/72—Eroding chemicals, e.g. acids

Definitions

  • the present invention relates generally to treating sandstone formations.
  • the present invention relates to methods of treating a sandstone formation by providing a treatment fluid including fulvic acid, any salt thereof, or any derivative thereof, or any combination thereof, and introducing the treatment fluid into the sandstone formation.
  • Treatment fluids including an acidic base fluid can be used in a number of subterranean operations including, for example, stimulation acidizing treatments/operations.
  • Treatments utilizing an acidic base fluid are especially challenging in some subterranean formations due to siliceous and aluminosilicate minerals commonly encountered therein. These silicon containing minerals can interact with an acidic base fluid to produce dissolved silicon species, which can subsequently precipitate at higher pH values (e.g., greater than about 3) as amorphous, gelatinous and/or colloidal silica.
  • HF hydrofluoric acid
  • aluminosilicates and silicates e.g., quartz, clays and feldspars
  • Hydrochloric acid (HCl) may be used in addition to HF in the treatment fluid to maintain a low pH as HF is spent during a treatment operation, thereby retaining certain dissolved species in a highly acidic solution.
  • HF can interact with the formation matrix, base fluids, or formation fluids to create precipitates, particularly in the presence of metal ions such as Al 3+ , Group 1 metal ions (e.g., Na + and K + ) and/or Group 2 metal ions (e.g., Mg 2+ , Ca 2+ , and Ba 2+ ), thereby leading to damage.
  • metal ions such as Al 3+ , Group 1 metal ions (e.g., Na + and K + ) and/or Group 2 metal ions (e.g., Mg 2+ , Ca 2+ , and Ba 2+ ), thereby leading to damage.
  • metal ions such as Al 3+ , Group 1 metal ions (e.g., Na + and K + ) and/or Group 2 metal ions (e.g., Mg 2+ , Ca 2+ , and Ba 2+ ), thereby leading to damage.
  • precipitation of various aluminum and silicon complexes can occur as a result of the reaction of the acid with the silic
  • the reaction of HF with a sandstone formation occurs in three stages.
  • clay in the formation reacts with HF to form fluorosilicic acid and aluminum fluoride.
  • silica gel is formed, and in the third stage, aluminum fluoride is formed.
  • Chelating agents are materials that are employed, among other uses, to control undesirable reactions of metal ions.
  • chelating agents are frequently added to matrix stimulation acids to prevent precipitation of solids as the acids react with the formation being treated. While typical chelating agents are capable of complexing metal ions, they often fail to complex silica, resulting in the precipitation of silica gel. These gel precipitates create damage to the formation, and are very difficult to remove from the formation.
  • FIG. 1 illustrates a land-based drilling and production system
  • FIG. 2 depicts a method of treating a sandstone formation according to embodiments of the present invention.
  • the methods of the present invention inhibit the formation of silica scale in a sandstone formation using the chelating agent fulvic acid, any salt thereof, or any derivative thereof, or any combination thereof.
  • sica scale refers to precipitated amorphous silica, precipitated gelatinous silica, precipitated colloidal silica, and/or hardened crusts of amorphous silica, precipitated silica, and/or precipitated colloidal silica.
  • fulvic acid acts as a single component system that can chelate several metal ions encountered in sandstone formations, including Al 3+ , Ca 2+ , and Mg 2+ , while also inhibiting precipitation of silica and/or silica scale.
  • metal ions encountered in sandstone formations, including Al 3+ , Ca 2+ , and Mg 2+
  • the fulvic acid slows, prevents, or inhibits silica polymerization and/or forms a soluble complex with silica to avoid silica gel formation.
  • the presence of several hydroxyl and carboxyl groups in fulvic acid make it very unique and helps in chelating different bivalent and trivalent ions, along with inhibiting the formation of silica scale.
  • a method of treating a sandstone formation includes providing a treatment fluid including an acidic base fluid and fulvic acid, any salt thereof, any derivative thereof, or any combination thereof, and introducing the treatment fluid into at least a portion of the sandstone formation.
  • the fulvic acid, any salt thereof, any derivative thereof, or any combination thereof inhibits formation of silica scale in the sandstone formation.
  • a “sandstone formation” refers to a formation composed of about 40% to about 98% sand/quartz particles, i.e., silica (SiO 2 ), bonded together by various amounts of cementing material including carbonate (calcite or CaCO 3 , dolomite, ankerite, siderite etc), aluminosilicates (xlays, feldspars, etc.), and silicates.
  • cementing material including carbonate (calcite or CaCO 3 , dolomite, ankerite, siderite etc), aluminosilicates (xlays, feldspars, etc.), and silicates.
  • the acidic base fluid includes an aqueous-based fluid.
  • the acidic base fluid includes one or more acids selected from the group consisting of hydrofluoric acid, hydrochloric acid, acetic acid, formic acid, citric acid, boric acid, lactic acid, methyl sulfonic acid, ethyl sulfonic acid, oxalic acid, malic acid, and maleic acid.
  • the one or more acids is present in the treatment fluid in an amount of about 0.01 percent to about 30 percent by volume of the treatment fluid.
  • the fulvic acid, any salt thereof, any derivative thereof, or any combination thereof is present in the treatment fluid in an amount of about 1 percent to about 20 percent by weight of the treatment fluid.
  • the method further includes complexing at least a portion of any metal ions present in the sandstone formation with the fulvic acid, any salt thereof, any derivative thereof, or any combination thereof.
  • Suitable metal ions include one or more of aluminum, calcium, and magnesium.
  • the treatment fluid has a pH of about 1 to about 3.
  • a pump is used to introduce the treatment fluid into at least a portion of the sandstone formation.
  • the method further includes after introducing the treatment fluid, allowing the treatment fluid to reside in the sandstone formation for a period of time, and removing the treatment fluid from the sandstone formation.
  • another method of treating a sandstone formation includes providing a treatment fluid including an aqueous fluid, hydrofluoric acid, hydrochloric acid, and fulvic acid, any salt thereof, any derivative thereof, or any combination thereof, and introducing the treatment fluid into at least a portion of the sandstone formation, wherein the fulvic acid, any salt thereof, any derivative thereof, or any combination thereof, inhibits formation of silica scale in the sandstone formation.
  • the hydrofluoric acid and hydrochloric acid is present in the treatment fluid in an amount of about 0.01 percent to about 30 percent by volume of the treatment fluid.
  • the fulvic acid, any salt thereof, any derivative thereof, or any combination thereof is present in the treatment fluid in an amount of about 0.01 percent to about 20 percent by weight of the treatment fluid.
  • the method further includes complexing at least a portion of any metal ions present in the sandstone formation with the fulvic acid, any salt thereof, any derivative thereof, or any combination thereof.
  • Suitable metal ions include one or more of aluminum, calcium, and magnesium.
  • the method further includes after introducing the treatment fluid, allowing the treatment fluid to reside in the sandstone formation for a period of time, and removing the treatment fluid from the sandstone formation.
  • a treatment fluid for acidizing a sandstone formation includes an aqueous fluid, hydrofluoric acid, hydrochloric acid, and fulvic acid, any salt thereof, any derivative thereof, or any combination thereof in an amount sufficient to inhibit formation of silica scale in the sandstone formation.
  • the treatment fluid has a pH of about 1 to about 3.
  • the hydrofluoric acid and hydrochloric acid is present in the treatment fluid in an amount of about 0.01 percent to about 30 percent by volume of the treatment fluid.
  • the fulvic acid, any salt thereof, any derivative thereof, or any combination thereof is present in the treatment fluid in an amount of about 0.01 percent to about 20 percent by weight of the treatment fluid.
  • treat refers to any subterranean operation that uses a fluid in conjunction with achieving a desired function and/or for a desired purpose. More specific examples of treatment operations include drilling operations, fracturing operations, gravel packing operations, acidizing operations, scale dissolution and removal, sand control operations, and consolidation operations.
  • Drilling and production system 10 utilized to produce hydrocarbons from wellbore 12 extending through various earth strata in an oil and gas formation 14 located below the earth's surface 16 .
  • Drilling and production system 10 may include a drilling rig or derrick 18 to perform various activities related to drilling or production, such as the methods described below.
  • drilling and production system 10 may include various types of tools or equipment 20 supported by rig 18 and disposed in wellbore 12 for performing these activities.
  • a working or service fluid source 52 such as a storage tank or vessel, may supply a working fluid 54 that is pumped to the upper end of tubing string 30 and flows through tubing string 30 .
  • Working fluid source 52 may supply any fluid utilized in wellbore operations, including without limitation, drilling fluid, slurry, acidizing fluid (e.g., HF, HCl, acetic acid, etc.), liquid water, steam, hydraulic fracturing fluid, propane, nitrogen, carbon dioxide or some other type of fluid.
  • a method of treating a sandstone formation includes using fulvic acid in a treatment fluid.
  • fulvic acid is an efficient and affordable chelating material that has good thermal stability and is produced from organic compost material.
  • fulvic acid is soluble in water in all pH conditions and can be used at any starting pH for treatments of sandstone formations.
  • fulvic acid is suitable for use in acid-sensitive subterranean formations in which strong acid treatment fluids cannot be effectively used for inhibiting or removing silica scale deposition.
  • sandstone formations are particularly sensitive to acids at high temperature and are often not amenable to acidizing treatments due to their propensity to deconsolidate and lose cementing material in the presence of strong acids.
  • sandstone formations are very prone to formation of silica scale due to their chemical makeup.
  • the presence of fulvic acid advantageously offers a much wider pH window for conducting subterranean operations.
  • the methods of the present invention complement the use of existing, strongly acidic treatment fluids by maintaining high levels of dissolved silicon in a treatment fluid that are otherwise only attainable at much lower pH values.
  • the use of fulvic acid is further advantageous because it can effectively coordinate with metal ions (e.g., Al 3+ ) even in the presence of dissolved silicon.
  • metal ions e.g., Al 3+
  • Al 3+ and soluble silicon species react to form insoluble aluminosilicate materials, thereby exacerbating an already challenging precipitation problem.
  • dissolved silicon refers to silicic acid, silanols, and other soluble silicon species.
  • certain metal ions are capable of reacting or complexing with fulvic acid, thereby potentially rendering them unsuitable for associating with dissolved silicon.
  • fulvic acid may be used in combination with one or more other chelating agents for the treatment of a sandstone formation.
  • Suitable chelating agents include methylglycine diacetic acid (MGDA), glutamic acid diacetic acid (GLDA), ⁇ -alanine diacetic acid, ethylenediaminedisuccinic acid, S,S-ethylenediaminedisuccinic acid, iminodisuccinic acid, hydroxyiminodisuccinic acid, polyamino disuccinic acids, N-bis[2-(1,2-dicarboxyethoxy)ethyl]glycine, N-bis[2-(1,2-dicarboxyethoxy)ethyl]aspartic acid, N-bis[2-(1,2-dicarboxyethoxy)ethyl]methylglycine, N-tris[(1,2-dicarboxyethoxy)ethyl]amine, N-methyliminodiacetic acid, iminodiacetic acid, imin
  • the treatment fluids include an acidic base fluid and fulvic acid, any salt thereof, or any derivative thereof, or any combination thereof.
  • the acidic base fluid includes HF and an additional acid, such as HCl or a weaker acid (e.g., acetic acid) to slow down the release rate of hydrogen ion to retard the HF reaction and to provide deep penetration in the sandstone formation.
  • the acidic base fluid is an aqueous-based fluid.
  • Aqueous-based fluids that are suitable include, for example, fresh water, saltwater (e.g., water containing one or more salts dissolved therein), brine, seawater, or combinations thereof.
  • the water can be from any source, provided that it does not contain significant quantities of materials that might adversely affect the stability and/or performance of the treatment fluid.
  • the aqueous-based fluids ideally should not contain significant quantities of metal ions that are reactive with fulvic acid or form an insoluble compound upon reaction with dissolved silicon.
  • the acidic base fluid includes one or more of HCl, HF, acetic acid, formic acid, citric acid, lactic acid, glycolic acid, sulfamic acid, tartaric acid, methanesulfonic acid, trichloroacetic acid, dichloroacetic acid, chloroacetic acid, fluoroboric acid, fluorophosphoric acid, hexafluorotitanic acid, fluorophosphoric acid and phosphoric acid.
  • suitable acid-generating compounds can also be used in the treatment fluid.
  • acid-generating compounds include, for example, esters, aliphatic polyesters, orthoesters, poly(ortho esters), poly(lactides), poly(glycolides), poly(s-caprolactones), poly(hydroxybutyrates), poly(anhydrides), and any copolymers thereof.
  • Other suitable acid-generating compounds include, for example, ethylene glycol monoformate, ethylene glycol diformate, diethylene glycol diformate, glyceryl monoformate, glyceryl diformate, glyceryl triformate, triethylene glycol diformate and formate esters of pentaerythritol. It should be noted that some of the above acids and acid-generating compounds are reported to complex dissolved silicon at high pH values.
  • the acid or acid-generating compound is present in the treatment fluid in an amount of about 1% to about 50% by volume of the treatment fluid.
  • the treatment fluid contains between about 1% to about 37% of acid by volume of the treatment fluid.
  • fulvic acid is present in the treatment fluid in an amount of about 1% to about 50% by weight of the treatment fluid.
  • the treatment fluid includes about 1% to about 20% of fulvic acid by weight of the treatment fluid.
  • the treatment fluids may also include one or more additives, such as gel stabilizers, fluid loss control additives, particulates, additional acids, corrosion inhibitors, catalysts, clay stabilizers, biocides, friction reducers, surfactants, solubilizers, pH adjusting agents, bridging agents, dispersants, flocculants, foamers, gases, defoamers, H 2 S scavengers, CO 2 scavengers, oxygen scavengers, scale inhibitors, lubricants, viscosifiers, and weighting agents.
  • additives such as gel stabilizers, fluid loss control additives, particulates, additional acids, corrosion inhibitors, catalysts, clay stabilizers, biocides, friction reducers, surfactants, solubilizers, pH adjusting agents, bridging agents, dispersants, flocculants, foamers, gases, defoamers, H 2 S scavengers, CO 2 scavengers, oxygen scavengers, scale
  • the method 200 includes providing a treatment fluid including an acidic base fluid and fulvic acid, any salt thereof, or any derivative thereof, or any combination thereof, in step 202 , and introducing the treatment fluid into at least a portion of the sandstone formation, wherein the fulvic acid, any salt thereof, or any derivative thereof, or any combination thereof, inhibits formation of silica scale in the sandstone formation in step 204 .
  • introducing includes pumping, injecting, pouring, releasing, displacing, spotting, circulating, or otherwise placing a fluid or material within a well, wellbore, or subterranean formation using any suitable manner known in the art.
  • the treatment fluids can be used in prevention methods to prevent the formation of precipitates such as, for example, those produced in conjunction with a HF acid treatment in a sandstone formation.
  • the treatment fluids may remove potentially damaging precipitates from the sandstone formation.
  • the treatment fluids may be allowed to reside in the sandstone formation for a period of time after being introduced thereto.
  • the fulvic acid in the treatment fluids increases an amount of dissolved silicon that is present in the treatment fluids while downhole.
  • the fulvic acid can effectively maintain any dissolved silicon in solution, thereby protecting the sandstone formation from damaging silica scale buildup.
  • the treatment fluids are removed from the sandstone formation.
  • removal of the treatment fluid can be performed after the dissolved silicon in the treatment fluid has reached a desired level or after a set shut-in period has passed.
  • a fresh batch of treatment fluid can be introduced to the sandstone formation to continue the treatment operation, or another type of treatment operation can be commenced.
  • the treatment fluids may be used as a pre-treatment to a fracturing treatment, especially in subterranean formations that contain different layers of sedimentary rock.
  • the treatment fluid is placed in a subterranean formation via a wellbore before a fracturing treatment.
  • the subsequent fracturing treatment can be a traditional fracturing treatment or an additional acidizing treatment directed at treating the particulate pack introduced during the fracturing operation.
  • the use of the treatment fluids may be considered a prevention mechanism to prevent the formation of potentially problematic precipitates.
  • the treatment fluids may be used to clean the wellbore area before bringing the well into final production.
  • Using such a treatment fluid can remove damage, blockages, debris, and natural clays in the formation, for example.
  • the fulvic acid in the treatment fluid can form a complex with at least a portion of any metal ions present in the sandstone formation.
  • fulvic acid can form a complex with aluminum ions in the presence of dissolved silicon to prevent the formation of aluminum scale.
  • metal ions such as, for example, Ca 2+ and Mg 2+ can also be complexed by fulvic acid. All of the aforementioned metal ions are normally present to some degree in sandstone formations.
  • Two test fluids were prepared to evaluate the ability of fulvic acid to inhibit the formation of silica scale.
  • 12 grams of sodium silicate (Na 2 SiO 3 .5H 2 O) was dissolved in 100 mL of water, and the pH of the first test fluid was adjusted to 1 using a 36.5% HCl solution.
  • the first test fluid was filtered using a 0.2 micron-size Nalgene® filter to remove insoluble materials.
  • To prepare the second test fluid 12 grams of sodium silicate (Na 2 SiO 3 .5H 2 O) and 1 gram of fulvic acid were dissolved in 100 mL of water, and the pH of the second test fluid was adjusted to 1 using a 36.5% HCl solution. Fulvic acid was added to the water prior to the sodium silicate.
  • the second test fluid was filtered using a 0.2 micron-size Nalgene® filter to remove insoluble materials.
  • the test fluid with fulvic acid effectively inhibited the formation of silica scale to as high a pH as 4, while the test fluid without fulvic acid exhibited silica scale formation at a pH of 2. Even at a pH of 5.6, where the test fluid without fulvic acid exhibited complete thick gel formation, the precipitate in the test fluid with fulvic acid was flowable.
  • Example 2 Additional tests using the first and second test fluids of Example 1 were performed to understand the effectiveness of silica scale inhibition at 190° F. As in Example 1, the pH of the two test fluids was gradually increased using MO-67TM pH control agent. The results of the tests are tabulated below in Table 2.
  • Test Fluid 1 Test Fluid 2 Time Time pH (minutes) Observation pH (minutes) Observation 2 5 Very thick 2 300 No mass precipitation 3 3 Height of 3 300 No thick mass is precipitation increased 5.4 4 Complete 5.4 300 Precipitation, thick gel but in formation flowable form
  • test fluid with fulvic acid inhibited the formation of silica scale up to a pH of 3, while the test fluid without fulvic acid exhibited silica scale formation at a pH of 2. Even at a pH of 5.4, where the test fluid without fulvic acid exhibited complete thick gel formation, the precipitate in the test fluid with fulvic acid was flowable.
  • test fluids were prepared to evaluate the ability of fulvic acid to chelate aluminum in the presence of dissolved silicon, to replicate conditions downhole.
  • 3 grams of sodium silicate (Na 2 SiO 3 .5H 2 O) was dissolved in 100 mL of water, and the pH of the solution was adjusted to 1 using a 36.5% HCl solution.
  • the resulting solution was filtered using a 0.2 micron-size Nalgene® filter to remove insoluble materials.
  • AlCl 3 aluminum chloride
  • test fluid with fulvic acid effectively inhibited the formation of aluminum scale up to a pH of 3.
  • aluminum scale was observed in the test fluid without fulvic acid at a pH of 2, 3, and 4. Even at a pH of 4, just a very small of aluminum scale was observed in the test fluid with fulvic acid.
  • compositions of Table 4 were prepared again and the process repeated using a Nalgene filter instead of Whatman® filter paper, grade 4.
  • Table 6 shows the initial weight measurements and resulting weight measurements after filtration.
  • fulvic acid is able to chelate ions one or more ions including Al +3 , Ca +2 , and Mg +2 in the presence of HF. Fulvic acid is also able to form a soluble complex with silica (e.g., Si 4+ ) in the presence of HF.
  • silica e.g., Si 4+

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Publication number Priority date Publication date Assignee Title
CN117965155A (zh) * 2024-03-29 2024-05-03 新疆中海科技有限公司 一种油田用酸化增产增注剂

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